College of Engineering Department of Chemical & Biomolecular Engineering. Presenting our. October 5-6, 2016 Clayton Hall Conference Center

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1 College of Engineering Department of Chemical & Biomolecular Engineering Center for Catalytic Science & Technology Presenting our 2016 Research Review October 5-6, 2016 Clayton Hall Conference Center Academy Street Colburn Laboratory Newark DE Phone: Fax:

2 Wednesday, October 5, 2016 Schedule of Events 2:45 PM REGISTRATION 3:00 PM Opening Remarks by Dr. Raul Lobo Director, Center for Catalytic Science & Technology Claire D. LeClaire Professor of Chemical Engineering 3:05 PM Eric Bloch, Assistant Professor of Chemistry & Biochemistry Small Molecule Activation with Metal-Organic Polyhedra 3:30 PM Stephanie Velardo CO 2 Reduction Using 3D Printed Flow Electrolysis 3:50 PM Jared Nash Effect of ph on the activity of hydrogen oxidation reaction/hydrogen evolution reaction over PtRu bimetallic catalysts 4:10 PM Yun Zhao Chlorine Recovery by Gasous HCl Electrolysis with Iron Redox Assisted Cathode 4:30 PM Wesley Luc Ultra-thin Electrocatalysts for Carbon Dioxide Reduction 4:50 PM Reception / Poster Session 6:00 PM Conclude for the day Thursday, October 6, :00 AM REGISTRATION 8:30 AM OPENING REMARKS / INTRODUCTION BY DR. RAUL LOBO SESSION I 8:40 AM Raul Lobo, Claire D. LeClaire Professor of Chemical Engineering Catalysis Innovation for Valorization of C1 molecules 9:10 AM Ali Mehdad Ethane Aromatization on Zinc Containing Zeolites 9:40 AM Huibo Sheng Iron-promotion of Cu/SiO 2 catalyst for furfural hydrodeoxygenation

3 Schedule of Events continue 10:10 AM Edward Schreiner High-pressure Conversion of C 5 -C 7 Alkanes for Aircraft Endothermic Cooling 10:40 AM BREAK / POSTER SESSION SESSION II 11:30 AM Srimoyee Dasgupta Copper(I) Catalyzed Enantioselective Alkynylation of Oxocarbenium and Iminium Ions to set Diaryl Tetrasubstituted Stereocenters 11:50 AM Erisa Saraci Cross metathesis of unsaturated carboxylic acids to terephthalic acid precursors 12:10 PM Kelsey Cobb Stereospecific Nickel-Catalyzed Suzuki Cross Couplings of Allylic Carboxylates to Set Quaternary Stereocenters 12:30 PM LUNCH SESSION III 1:45 PM Basudeb Saha, Associate Director of Research, Catalysis Center for Energy Innovation Towards sustainable catalytic oxidation for dicarboxylic acid 2:15 PM Maura Koehle Production of para-methylstyrene and para-divinylbenzene from furanic compounds 2:35 PM Matt Gilkey Metal-Free Production of Adipic Acid via Hydrogenolysis of Biomass-Derived Tetrahydrofuran-2,5-Dicarboxylic Acid in Organic Acid Solvents 2:55 PM Efterpi Vasileiadou Lewis acid catalyzed formaldehyde-olefin condensation: a valuable route for C-C formation 3:15 PM CLOSING REMARKS BY DR. LOBO 3:30 PM CONFERENCE CONCLUDES Poster Presentation Abstracts Page 20

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5 Research Review Presentation

6 CCST 2016 RESEARCH REVIEW CO 2 Reduction Using 3D Printed Flow Electrolysis Stephanie M. Velardo Advisor: Joel Rosenthal The development of inexpensive electrolyzer platforms capable of efficient and rapid reduction of CO 2 to CO provide a route to solar fuel production when driven by renewable electricity generated from a PV assembly. Our laboratory has developed a bismuth-carbon monoxide evolving catalyst (Bi-CMEC) using an electrodeposition strategy. This Bi-CMEC catalyst promotes the conversion of CO 2 to CO at rates and selectivities comparable to those historically observed for precious metals such as silver and gold. In an effort to improve the scalability of the Bi-CMEC platform we have developed a streamlined method by which solutions of Bi 3 + salts may be drop cast onto large two-dimensional electrode supports. These modified electrodes have been utilized in conjunction with 3D-printed flow cell assemblies to enable the large scale production of CO. This new CO 2 electrolyzer may be directly integrated with PV assemblies to drive to production of CO using solar energy and serves to underscore the feasibility of rapid solar fuel generation. Page 5

7 CCST 2016 RESEARCH REVIEW Effect of ph on the activity of hydrogen oxidation reaction/hydrogen evolution reaction over PtRu bimetallic catalysts Jared Nash Advisor: Bingjun Xu, Yushan Yan Hydrogen proton exchange membrane fuel cell (PEMFC) powered automobiles have become commercially available, but are still too expensive. Hydroxide exchange membrane fuel cells (HEMFCs) offer the possibility of cheaper non-precious metal catalysts. However, the hydrogen oxidation reaction (HOR) and hydrogen evolution reaction (HER) are significantly slower in base than in acid for Pt, Pd, Ir, and Rh 1-4. PtRu shows higher HOR/ HER activity than Pt 5, 6, so understanding the mechanism of the HOR/HER on PtRu is key to developing nonprecious metal catalysts for HEMFCs. Using the rotating disk electrode, bimetallic PtRu showed a minimum in the HOR/HER activity, ph relationship, not seen on monometallic catalysts. The hydrogen binding energy and the hydroxide binding energy measured from the hydrogen underpotential desorption peak and the CO stripping peak, respectively, did not change significantly with ph. Leaching Ru from the catalyst, it was found that the HOR/ HER activity of PtRu remains approximately constant while the Ru content is reduced. Only after a significant amount of Ru has been removed does the activity change. The charge transfer coefficient, α, decreases with the Ru content going from 0.8 to 0.5. Fitting the kinetic data with the dual pathway model 7 shows that below ph 11, the Heyrovsky and Volmer reaction barriers are comparable and above ph 11, the Volmer step becomes rate determining. It is proposed that Ru can align more oxygen species on the surface giving water a more favorable orientation for the Volmer step to proceed, which results in an increase in activity. References: 1. Sheng, W., et al., Nature communications 2015, Zheng, J., et al., Science Advances 2016, 2 (3). 3. Durst, J., et al., J Electrochem Soc 2015, 162 (1), F190-F Sheng, W., et al., J Electrochem Soc 2010, 157 (11), B Wang, Y., et al., Energy Environ. Sci. 2014, 8 (1), Wang, J. X., et al., Scientific Reports 2015, 5, Elbert, K., et al., ACS Catal 2015, Page 6

8 CCST 2016 RESEARCH REVIEW Chlorine Recovery by Gasous HCl Electrolysis with Iron Redox Assisted Cathode Yun Zhao Advisor: Yushan Yan Chlorine is used to synthesize numerous consumer products and useful intermediates. [1] Chlorination of alkanes or aromatics is a substitution reaction with hydrogen, for which only half of the chlorine atoms are actually used to produce chloro-organics, the other half being lost as waste HCl gas or recovered as low-value HCl aqueous solution. Today, the global by-production of HCl totals 9.3 million tons per year, when only the synthesis of polyurethane, chloromethane, and polycarbonate is considered. At present, only 15% of this HCl byproduct is recycled, leaving an unrealized Cl 2 regeneration market of $2.4 billion per year (based on the current price of Cl 2 : $315/ton). [2] Currently, the dominant commercial processes today are electrochemical because of the simple modular design and milder operating conditions electrolyzers offer. [3] Typical processes feed waste aqueous HCl solution to the anode and utilize a hydrogen evolution (HEC, Equation 1) or oxygen depolarization (ODC, Equation 2) cathode, generating hydrogen or water, respectively, in addition to Cl 2. HCl Cl 2 + H 2 (1) 4 HCl + O 2 2 Cl 2 +2 H 2 O (2) Despite the increasing demand for Cl 2, current HCl recycling technologies are not economical enough to deploy into more of this multi-billion-dollar market. Herein, we propose an iron reduction cathode (IRC) based gaseous HCl electrolyzer system to regenerate chlorine from waste hydrogen chloride at low temperature. At the anode, HCl gas is oxidized to generate chlorine and protons, at the cathode, Fe 3+ is electrochemically reduced to form Fe 2+. Subsequently, Fe 2+ is chemically oxidized to Fe 3+ by oxygen in a reactor external to the electrolytic cell. Regeneration Fe 2+ is recycled to the electrolyzer. Due to high standard potential (p o, 0.77 V SHE ) and fast kinetics (exchange current density, i 0, of ~10 2 A/cm 2 on glassy carbon, no catalyst was required), [4] IRC offers substantial benefits over alternative commercial HEC and ODC cathodes. Taking advantage of IRC, a much lower cell voltage is achieved: 0.67 V vs V (with ODC) and 1.22 V (HEC) at a typical current density of 4 ka/ cm 2. Compared to the commercial HEC or ODC-based HCl electrolysis processes, it will save 45 50% of energy consumption approximately. Moreover, without the need for a precious metal cathode catalyst and a costly thick membrane, the captital cost can be reduced by 40% 50% (IRC: $2,640/m 2 vs. HEC: $4,339/m 2 and ODC: $5,034/ m 2, estimated with 4 ka/m 2 and current materials prices). [1] J. Perez-Ramirez, C. Mondelli, T. Schmidt, et al, Energy & Environmental Science, 2011, 4, [2] ThyssenKrupp, HCl electrolysis brochure. [3] I. G. Martinez, T. Vidaković-Koch, R. Kuwertz, et al, Electrochimica Acta, 2014, 123, 387. [4] Y. H. Wen, H. M. Zhang, P. Qian, et al, Electrochimica Acta, 2006, 51, Page 7

9 CCST 2016 RESEARCH REVIEW Ultra-thin Electrocatalysts for Carbon Dioxide Reduction Wesley Luc Advisor: Dr. Feng Jiao Converting greenhouse gas carbon dioxide (CO 2 ) to value-added chemicals is an appealing approach to tackle CO 2 emission challenges. The chemical transformation of CO 2 requires a suitable catalyst that can lower the activation energy barrier, thus minimizing the energy penalty associated with the CO 2 reduction reaction. Firstrow transition metals are potential candidates as catalysts for electrochemical CO 2 reduction; however, their high oxygen affinity makes them easy to be oxidized, which could, in turn, strongly affect the catalytic properties of metal-based catalysts. In this work, we propose a new strategy to synthesize ultra-thin electrocatalysts using a core-shell nanoarchitecture that contains a bimetallic core responsible for high electronic conductivity and an ultra-thin partially oxidized shell responsible for catalytic CO 2 conversion. This concept was demonstrated by a series of core-shell electrocatalysts with a Ag-Sn bimetallic core and a partially oxidized SnO x shell. At an optimal SnO x shell thickness of ~1.7 nm, the catalyst exhibited a high formate Faradaic efficiency of ~80% and a formate partial current density of ~16 ma cm -2 at -0.9 V vs. RHE, a remarkable performance in comparison to state-of-art formate-selective CO 2 reduction catalysts. Page 8

10 CCST 2016 RESEARCH REVIEW Ethane Aromatization on Zinc Containing Zeolites Ali Mehdad Advisor: Raul F. Lobo Benzene, toluene and xylenes (BTX) are produced by naphtha reforming, a process in which naphtha represents about 80% of BTX production cost (1). The current oversupply of ethane makes ethane a relatively inexpensive feedstock, compared to naphtha (2), for the production of aromatics. Different metals have been investigated for aromatization of light alkanes and among them Zn and Ga incorporated into aluminosilicate zeolites have showed the best results. These two metals show good dehydrogenation activity without catalyzing hydrogenolysis (3). Conversion of ethane on zinc containing zeolites has been investigated at 500 C and atmospheric pressure. Initial tests indicate that H + /ZSM-5 and a zinc-containing small-pore zeolite (Zn/chabazite, SiO 2 /Al 2 O 3 =6) do not catalyze the aromatization reaction; zinc-containing large-pore zeolite (Zn/BEA, SiO 2 /Al 2 O 3 =25) has lower reaction rates as compared to that of zinc-containing medium-pore ZSM-5 zeolites (Zn/ZSM-5, SiO 2 /Al 2 O 3 = 23). Zn/ZSM-5 showed different reaction rates and selectivity for conversion of ethane or ethylene depending on the amount of zinc, preparation technique and SiO 2 /Al 2 O 3 of the zeolite. If ethane is the feed, ethylene or aromatics product selectivity will be predominant and if ethylene is the feed, ethane or aromatics product selectivity will be predominant. Zinc sites are necessary for ethane activation and increasing the amount of zinc in the sample increases overall reaction rate. At SiO 2 /Al 2 O 3 =23, samples prepared by ion exchange can contain up to 2.5%w/w of zinc. These samples showed lower deactivation rates and higher selectivity towards ethylene than aromatics, as compared to samples containing 5%w/w Zn/ZSM-5 prepared by incipient wetness impregnation (IWI). Diffusereflectance UV-vis spectra show that conventional oven drying of Zn/ZSM-5 (prepared by IWI) will form larger ZnO clusters as compared to the freeze-dried sample. Lewis sites (cationic zinc sites) and BrØnsted acid sites (BAS) both can catalyze the oligomerization of ethylene. Zinc sites in the ZSM-5 are also responsible for the dehydrogenation of naphthenic intermediates. Samples with higher concentrations of BAS, deactivate faster, and carbon deposition inside the zeolite pores is identified as the main source of deactivation. Small ZnO clusters can catalyze the dehydrogenation, but not the aromatization, as Zn/silicalite-1 was active for ethane dehydrogenation to ethylene, while it showed low reaction rates for conversion of ethylene. References 1. Guisnet M, Gnep NS, Alario F. Aromatization of short chain alkanes on zeolite catalysts. Applied Catalysis A: General. 1992;89(1): Short-Term Energy Outlook. US Energy Information Administration Hagen A, Roessner F. Ethane to Aromatic Hydrocarbons: Past, Present, Future. Catalysis Reviews. 2000;42(4): Page 9

11 CCST 2016 RESEARCH REVIEW Iron-promotion of Cu/SiO 2 catalyst for furfural hydrodeoxygenation Huibo Sheng Advisor: Raul F. Lobo Selective hydrogenation of biomass-derived compounds is often necessary for the valorization of compounds such as this form of renewable carbon is oxidized relative to the most important commodity organic chemicals such as ethylene, methanol, etc. A catalyst that is inexpensive, stable and selective is desired to accomplish such hydrogenations. As a derivative of lignocellulose, [1] furfural is a platform chemical that can be upgraded to a variety of valuable organic chemicals and biofuels. [2] Several cellulosic ethanol plants have been opened in the Midwest of the USA with 30-million gallon ethanol annual production capacity, [3] and since C5 sugar streams are not ideal for fermentation, these could be used instead for the preparation of furfural. The hydrodeoxygenation (HDO) of furfural is a promising process to remove excess oxygen and increase energy density and stability. The product, 2-methylfuran, for example, is an excellent biofuel candidate or additive. The challenge of this process is the stable hydrogenation of the side carbonyl group only, leaving the furan ring untouched. Silica supported copper is a mild hydrogenation catalyst that is selective for the hydrogenation of the carbonyl group of furfural to furfuryl alcohol. We have found that iron-containing Cu-based catalyst show much higher reactivity and very high selectivity towards 2-methylfuran (85%+). It is of interest to understand the structural and chemical effects of the iron promotion (0.15% w/w) over the Cu catalyst (1% Cu w/w) and characterize the species responsible for the high hydrogenation performance. Our investigations indicate that after the catalyst is pre-treated in hydrogen, copper is fully reduced while iron is only partially reduced (a mixture of Fe III and Fe II is observed). An in situ DRIFT study suggests that Fe II species are present on the catalyst surface, as indicated by the adsorption of NO. [4] 1. G. W. Huber, S. Iborra, A. Corma, Chemical Reviews 2006, 106, J.-P. Lange, E. van der Heide, J. van Buijtenen, R. Price, Chemsuschem 2012, 5, U. S. Energy Information Administration (EIA), Vol. 2016, H. Sheng, R. F. Lobo, Chemcatchem, 2016 (accepted). Page 10

12 CCST 2016 RESEARCH REVIEW High-pressure Conversion of C 5 -C 7 Alkanes for Aircraft Endothermic Cooling Edward P. Schreiner Advisor: Raul F. Lobo Practical use of hypersonic planes (> Mach 5) has been hindered by overheating of aircraft engine and electronic components, caused by high fuel combustion rates and air friction 1. Current military aircraft can use jet fuel as a heat sink, but future hypersonic aircraft will exceed the cooling capacity of the fuel 2,3. Cooling capacity can be increased through use of so-called endothermic fuels, which remove thermal energy produced by the aircraft through endothermic chemical reactions 4,5. Cracking reactions are endothermic and the solid acid zeolite, H-[Al]ZSM-5, was chosen to catalyze these reactions as it is known to yield light olefins with high selectivity in fluidized catalytic cracking units 6. It was found, however, that secondary bimolecular reactions on H-[Al]ZSM-5 controlled product distribution and reduced reaction endothermicity 7. Subsequently, supported molybdenum carbide catalysts were investigated as they can react with numerous hydrocarbons producing olefins 8. A number of pure and supported molybdenum carbides were investigated for the dehydrogenation of n-pentane. Two samples provided the highest reactivity and selectivity toward pentenes: Mo/H-[B]ZSM-5 (zeolite support) and Mo/Al 2 O 3. These two catalysts exhibited an induction period, with the highest reaction rates observed 1.5 h after the start of the reaction. This increase in reactivity indicates that the most active form of the catalyst was formed in the reactor by interaction with the reactant. Slow deactivation was observed over the 5 h on stream investigated, but unlike the other catalysts tested, the selectivity of the dehydrogenation product from the zeolite support did not change with time on stream. Dehydrogenation of n-hexane and n-heptane were also tested on the most active catalysts. The Mo/H-[B]ZSM-5 catalyst showed the highest conversion of all the catalysts investigated, while maintaining the same high selectivity towards the dehydrogenation product as Mo/Al 2 O 3. Furthermore, by using H-[B]ZSM-5, the undesirable secondary bimolecular reactions observed in acidic H-[Al]ZSM-5, which include oligomerization and dehydrocyclization reactions, were suppressed, preserving the desired olefinic product and increasing reaction endothermicity. 1. Lander, H., Nixon, A.C. (1971) Journal of Aircraft 8: Widegren, J.A., Bruno, T.J. (2009) Energy Fuels 23: Chung H.S., Chen, C.S.H., Kremer, R.A., Boulton, J.R. (1999) Energy Fuels 13: Gascoin, N., Abraham, G., Gillard, P. (2010) J Analytical and Applied Pyrolysis 89: Kim, J., Hyeon, D.H., Park, S.H., Chun, B.H., Jeong, B.H., Han, J.S., Kim, S.H. (2014) Catalysis Today 232: Corma, A. (1995) Chem. Rev. 95: Schreiner, E., Teketel, S., Lobo, R. (2015) New Journal of Chemistry. 40: Solymosi, F., Nemeth, R., Ovari, L., and Egri, L. (2000) J. of Catalysis 195: Page 11

13 CCST 2016 RESEARCH REVIEW Copper(I) Catalyzed Enantioselective Alkynylation of Oxocarbenium and Iminium Ions to set Diaryl Tetrasubstituted Stereocenters Srimoyee Dasgupta Advisor: Mary P. Watson The primary focus of our research group is to develop new synthetic methodologies that utilize the power of transition metal catalysis. Transition metal catalysis has transformed the field of synthetic organic chemistry by enabling new and highly efficient reactions with exceptional control over regio- and enantioselectivity. Most transition metal catalysis relies heavily on neutral electrophiles, but we envisioned that it could also be efficiently used with cationic electrophiles to solve significant, long-standing challenges in organic synthesis. In particular, few methods are available for enantioselective additions to cyclic ketoxocarbenium and ketiminium ions to form diaryl, tetrasubstituted stereocenters. Harnessing our success in developing a copper-catalyzed addition of terminal alkynes to oxocarbenium ions to deliver isochromans with tertiary stereocenters, 1 we have now developed a highly enantioselective, copper(i)/pybox-catalyzed addition of terminal alkynes to isochroman ketals to set diaryl-substituted quaternary stereocenters. 2 The success of this transformation relies on identification of a Cu/PyBox catalyst capable of distinguishing two aryl substituents on the forming stereocenter, which differ predominantly in their freedom of rotation and by their relationship to the oxygen substituents (alkyl vs lone pair). This highly challenging transformation enables the efficient conversion of readily available, racemic ketals to high-value, enantioenriched isochroman products, presumably via prochiral oxocarbenium ion intermediates. Reaction optimization, scope of both the ketal and alkyne, and elaboration of products will be presented. We were also able to use this potent copper(i)/pybox catalyst to develop an enantioselective, copper(i)- catalyzed alkynylation of ketiminium ion intermediates to deliver tetrahydroisoquinolines with tetrasubstituted α stereocenters in high yields and enantioselectivities. Select substrate scope and elaboration of products in this method will also be presented. We are currently investigating how the chiral copper/pybox catalyst imparts enantioselectivity in these reactions. Initial mechanistic experiments elucidating the structure of the active catalyst as a dicopper acetylide species and further reactions inspired by these methods will also be discussed. 1. (a) Maity, P.; Srinivas, H. D.; Watson, M. P. J. Am. Chem. Soc. 2011, 133, 17142; (b) Srinivas, H. D.; Maity, P.; Yap, G. P. A.; Watson, M. P. J. Org. Chem. 2015, 80, Dasgupta, S.; Rivas, T.; Watson, M. P. Angew. Chem. Int. Ed. 2015, 54, Page 12

14 CCST 2016 RESEARCH REVIEW Cross metathesis of unsaturated carboxylic acids to terephthalic acid precursors Erisa Saraçi Advisor: Raul F. Lobo Terephthalic acid is essential for the preparation of a variety of polyester fibers and is largely produced via the catalytic oxidation of petroleum-derived p-xylene [1]. The ongoing exchange of naphtha crackers with shale gas crackers is causing a shortage in some aromatics species, such as p-xylene [2]. As a consequence, alternative and sustainable routes to produce terephthalic acid from biomass derivatives, e.g. bio-sourced sorbates [3], are highly desirable. In the last decade, Ru-catalyzed olefin metathesis, and in particularly cross-metathesis, has become an important tool for the formation of carbon carbon bonds and the formation of valuable organic molecules [4]. We have investigated the ruthenium-catalyzed cross metathesis of sorbates with acrylates to form diester muconates. In a subsequent step, the reaction between alkyl muconates and ethylene affords the aromatization to dialkyl terephthalate. The effect of alkyl substituents and solvents was investigated over various organometallic ruthenium-based catalysts to increase conversion and selectivity towards the alkyl muconates. Conversions of up to 35% and 20% yields were achieved within the first hour of reaction with very low amounts (0.5 mol.%) of ruthenium-based catalyst containing a N-heterocyclic carbene (NHC) ligand. The conversion and yield can be increased by augmenting the catalyst amount. If a solvent was used, the cross metathesis products were formed in higher yields with the use of more polar solvents, i.e. CH2Cl2. To develop a greener process, the acrylate reactant was used in excess with no other solvent added. By using reactants (sorbates and acrylates) with smaller alkyl substituents the yield of cross metathesis products was favored, and ultimately the diester muconate precipitated in an easily recoverable solid form. Upon further development, this route for obtaining di-ester muconates, may provide a sustainable alternative for producing biomass derived precursors to polyethylene terephthalate (PET) and other valuable polyesters. References 1. Roge rio A. F. Toma s, Joa o C. M. Bordado, and Joa o F. P. Gomes. Chem. Rev. 113 (2013) C. Luke Williams, Chun-Chih Chang, Phuong Do, Nima Nikbin, Stavros Caratzoulas, Dionisios G. Vlachos, Raul F. Lobo, Wei Fan, and Paul J. Dauenhauer. ACS Catal. 2 (2012) Sandrine Be rard, Christophe Valle e, and Damien Delcroix. Ind. Eng. Chem. Res. 54 (2015) Georgios C. Vougioukalakis, and Robert H. Grubbs. Chem. Rev. 110 (2010) 1746 Page 13

15 CCST 2016 RESEARCH REVIEW Stereospecific Nickel-Catalyzed Suzuki Cross Couplings of Allylic Carboxylates to Set Quaternary Stereocenters Kelsey M. Cobb Advisor: Mary P. Watson Asymmetric preparation of quaternary stereocenters remains an important goal and longstanding challenge in organic chemistry. Enantioselective or enantiospecific substitution of allylic electrophiles offers entry to the preparation of enantioenriched quaternary sterocenters. Allylic electrophiles have previously been utilized to prepare quaternary stereocenters, but these reactions typically rely on harsh air-sensitive nucleophiles such as Grignards or zinc reagents, and/or are limited to the formation of terminal alkenes or to specific substitution requirements. Our group has previously developed stereospecific Suzuki-Miyaura arylations of benzylic and allylic electrophiles to deliver products with tertiary stereocenters. We envisioned that this strategy may also enable the asymmetric synthesis of quaternary stereocenters. Our substrates are derived from allylic alcohols, which are ideal candidates for enantiospecific reactions due to their easy accessibility in high enantiopurity. In addition, our coupling partners are aryl boroxines, which are functional group tolerant and allow for a broad substrate scope. We will report our efforts to develop the allylic arylation to set quaternary stereocenters via Suzuki-Miyaura cross-couplings. Optimization, scope, and mechanistic understanding of this reaction will be presented. Page 14

16 CCST 2016 RESEARCH REVIEW Towards sustainable catalytic oxidation for dicarboxylic acid Basudeb Saha Catalysis Center for Energy Innovation, University of Delaware, Newark, DE Catalytic oxidation plays a critical role in the production of high volume commodity chemicals that are used for the manufacture of thousands of household consumable goods. One example is purified terephthalic acid (PTA), representing more than 100 billion pounds annual production by aerobic oxidation of para-xylene (px) in acetic acid by homogeneous bromide containing catalyst. This oxidation process is corrosive and generates environmentally hazardous methyl bromide. Thus, an overarching goal is the development of oxidation processes that can be operated in water without utilizing hazardous chemicals. However, immiscibility of px in water poses a barrier to this effort. Recently, heterogeneous catalyzed aerobic oxidation of renewable substrates such as 5-hydroxymethylfurfural (HMF) and glucose to the corresponding dicarboxylic acids in water has been emerged as an effective alternate strategy. While significant technological advancement has been achieved in HMF oxidation over the past years enabling >95% 2,5-furandicarboxylic acid (FDCA) yield, efficient oxidation of glucose to glucaric acid has been proven to be a challenge due to slow and difficult oxidation of gluconic acid, an intermediate oxidation product of glucose. We studied aerobic oxidation of glucose to glucaric acid using activated carbon, SiO2 and Al2O3 supported Pt catalysts in water.1 Through systematic optimization of the reaction conditions in a wide range of ph, O2 pressure, temperatures and glucose to Pt molar ratio, we achieved a maximum 74% glucaric acid yield with Pt/C at initial ph of 7.2, which is the highest reported yield of glucaric acid to date. C C bond scission of glucaric acid in basic ph results in low carbon chain carboxylic acids. Higher temperatures and higher Pt loadings cause degradation of glucaric acid, resulting in lower yields. Recyclability and characterization studies reveal that the catalyst is stable after five cycles with no sign of Pt leaching into the solution. Reference 1. J. Lee, B. Saha and D. G. Vlachos, Green Chemistry, Page 15

17 CCST 2016 RESEARCH REVIEW Production of para-methylstyrene and para-divinylbenzene from furanic compounds Molly Koehle Advisor: Raul Lobo Of the three isomers of methylstyrene, para-methylstyrene is highly desirable because it yields polymers with superior properties over polystyrene and mixed poly-methylstyrene [1]. However, controlling the substitution of methylstyrene via direct acylation or alkylation of toluene is difficult because even though the para isomer is favored, meta and ortho isomers are also formed [1, 2], and separation of the isomer mixture is very difficult due to their nearly identical properties. The Diels-Alder cycloaddition and dehydration of substituted furans with ethylene is a plausible route to p-methylstyrene since it is inherently selective to para aromatic species. We have successfully developed a three-step catalytic route to p-methylstyrene from methylfuran (Scheme 1) at high yield and very high isomer selectivity. The process uses Friedel-Crafts acylation, selective reductions with hydrogen and Diels-Alder cycloaddition with ethylene. The raw materials furans, ethylene and acetic acid can all be derived from biomass [3,4], thus allowing green styrene production from renewable carbon sources. This approach has also been extended to the production of p-divinylbenzene. Scheme 1: Production of para-methylstyrene from methylfuran References 1. W.W. Kaeding and G.C. Barile, in: B.M. Culbertson and C.U. Pittman, Jr. (Eds.), New Monomers and Polymers, Plenum Press, New York, NY, 1984, pp Aromatic Substitution Reactions A.A. Rosatella; S.P. Simeonov; R.F.M. Frade, R.F.M..; C.A.M. Afonso, Green Chem., 13 (2011) C.H. Christensen; J. Rass-Hansen; C.C. Marsden; E. Taarning; K. Egeblad, ChemSusChem, 1 (2008) 283. Page 16

18 CCST 2016 RESEARCH REVIEW Metal-Free Production of Adipic Acid via Hydrogenolysis of Biomass-Derived Tetrahydrofuran-2,5- Dicarboxylic Acid in Organic Acid Solvents Matthew J. Gilkey Advisors: Bingjun Xu and Dionisios G. Vlachos Adipic acid (AA) is an essential precursor in the polymer industry, primarily for its use in the synthesis of Nylon-66. However, AA s current production method, which relies on the selective oxidation of petroleumderived cyclohexane, contains several drawbacks including the emission of N 2 O, a potent greenhouse gas. In effort to create a sustainable route to AA, significant research effort has been dedicated to develop pathways from biomass-derived platform chemicals through selective hydrodeoxygenation. Of particular interest is the hydrogenolytic ring opening of tetrahydrofuran-2,5-dicarboxylic acid (THFDCA) to AA. By reacting THFDCA in a mixture of hydriodic acid (HI) and molecular hydrogen in an organic acid solvent, an AA yield of up to 87% yield can be achieved in the absence of a metal catalyst. Through a combination of experimental and theoretical contributions, we reveal key mechanistic insights into the hydrogenolysis mechanism, noting that the nature of the solvent is critical in maintaining high ring opening activity. We have subsequently performed kinetic measurements to determined reaction orders of THFDCA, HI, and molecular hydrogen, where each component in the reaction mixture create an intricate recipe to synergistically remove C-O bonds in THFDCA to form AA. Page 17

19 CCST 2016 RESEARCH REVIEW Lewis acid catalyzed formaldehyde-olefin condensation: a valuable route for C-C formation Efterpi (Efi) Vasileiadou Advisor: Prof. Raul Lobo New carbon-carbon bonds can be formed via the ene reaction, a pericyclic process between an alkene having an allylic hydrogen atom (an ene ) and an electron-deficient multiple bond (an enophile) to form two sigma-bonds with transposition of the pi-bond [1] (see Scheme 1). Scheme 1 Schematic Interaction in ene reaction Prins reaction (Carbonyl-ene reaction) is an example of the ene reaction referring to condensation of formaldehyde with olefins [2]. The commercial availability of lower olefins, especially those formed by on-purpose methods from their corresponding alkanes (C3 and C4), coupled with the versatility of formaldehyde as a one-carbon electrophile make this reaction potentially important. Prins condensation can form unsaturated alcohols, diols, alkyl dioxanes, pyran skeleton compounds and dienes. The reaction is an acid catalyzed addition of aldehydes to olefins and is traditionally catalyzed by homogeneous mineral acids such as sulphuric acid or homogeneous Lewis acids like SnCl 4, BF 3 and ZnCl 2 [3]. We have investigated solid Lewis acid catalysis for the reaction. Initially, acidic zeolite Beta catalysts have been synthesized and evaluated in the condensation of formaldehyde propylene. Specifically, framework Sn-, Zr-beta, and Zn-Beta the last prepared by ion exchange were prepared and characterized. The catalytic activity was tested by autoclaving formaldehyde and propylene using an appropriate solvent at a temperature range of C. We have found that Zn-Beta is the most active catalyst for this reaction. Different reaction pathways are followed producing valuable products. The product spectra can be divided into two categories; compounds with four carbon atoms (3-buten-1-ol and 1,3-butadiene) and compounds having five carbon atoms (1,3-Dioxane, 4-methyl-, tetrahydro-4h-pyran-4-ol and 3,6-dihydro-2H-pyran). The dominant reaction route in the presence of Zn-Beta when reacting formaldehyde with propylene is 3,6-dihydro-2H-pyran; a five carbon product formed via Prins cyclization-sequential reaction of formaldehyde with 3-buten-1-ol. Aiming to induce shape selectivity and minimize the routes forming five carbon compounds we synthesized and tested a series of different pore size Zn-exchanged zeolites. Our purpose was to drive the reaction towards 3-buten-1-ol which upon dehydration forms 1,3-butadiene; an important chemical used in the production of synthetic rubber. Zn-ZSM-5 showed very promising results as 3-buten-1-ol is selectively (60% selectivity) formed, while the extent to five carbon products considerably decreased. The reaction between formaldehyde and isobutene was also studied in the presence of Zn-ZSM-5. In this case the target product is 3-methyl-3-buten-1ol which dehydrates to isoprene; the synthetic monomer of natural rubber. The catalyst was highly selective achieving up to 92% selectivity. Most importantly, we also formed isoprene in one-step showing great potential of this process. [1] M. Yamanaka and K. Mikami, Helvetica Chimica Acta, 85 (2002) 4264 [2] P. C. Bloys van Treslong Prins, Chem. Weekkbl. 1919, 1510 [3] D. R. Adams and S. P. Bhatanagar, Synthesis 10 (1977) 661 Page 18

20 Poster Presentations

21 Chen-Yu Chou Reverse Water-Gas Shift Iron Catalyst Derived from Fe 3 O 4 Page 20 Srimoyee Dasgupta Copper(I) Catalyzed Enantioselective Alkynylation of Oxocarbenium and Iminium Ions to set Diaryl Tetrasubstituted Stereocenters Page 21 Saikat Dutta Hydrodeoxygenation of Long-Carbon Trifurylmethane into Jet Fuels with Pd/C-Hf(OTf) 4 Page 22 Jiayi Fu Heterogeneous Catalytic Route towards Succinic Acid from Biorenewable Tartaric Acid Page 23 Matthew Gilkey Mechanistic Insights into the Ring Opening of Biomass-Derived Tetrahydrofuran-2,5-Dicarboxylic Acid to Adipic Acid Page 24 Nicholas Gould Solvent Effects on Zeolites: Liquid Phase FTIR Extinction Coefficient Determination Page 25 Geun Ho Gu Group Contribution Method for Solvation Free Energy Estimation of Aliphatic Alcohols on Metal Surface Page 26 Glen Jenness Reaction Pathways and Intermediates in Selective Ring Opening of Biomass-Derived Heterocyclic Compounds by Iridium Page 27 Alexander Mironenko Metal/Metal Oxide Cooperativity for Selective C-O Bond Activation Page 28 Marcel Nunez Optimization of transition metal catalyst structure for the oxygen reduction reaction Page 29 Taha Salavati-fard Catalytic Effects of Transition Metal Oxide Surfaces on Diels-Alder Cycloaddition between Furan and Methyl Acrylate: A DFT Study Page 30 Huibo Sheng Methane non-oxidative coupling to ethylene on Mo 2 C/[B]ZSM-5 Page 31

22 CCST 2016 RESEARCH REVIEW Reverse Water-Gas Shift Iron Catalyst Derived from Fe 3 O 4 Chen-Yu Chou Advisor: Raul F. Lobo CO 2 is the most widely known global warming gas. Conversions of CO 2 to fuels and chemicals offer opportunities to mitigate the increasing CO 2 buildup. Hydrogenation of CO 2, particularly reverse water-gas shift (RWGS) reaction, to intermediate chemicals or fuels such as CO is a feasible and valuable process with this regard [1]. One of the major challenges is that the conventional Cu-ZnO catalyst is temperature-sensitive while high temperature in endothermic RWGS reaction is preferable[2,3]. In this work, unsupported iron oxides, specifically magnetite (Fe 3 O 4 ), were used as a catalyst for the RWGS reaction at temperatures between 723 K and 773 K. This catalyst exhibited fast catalytic CO formation rate (35.1 mmol h -1 g -1 ), high turnover frequency ( s -1 ), high CO selectivity (>99%), and high stability. Reaction rates over Fe 3 O 4 catalyst displayed a strong dependence on H 2 partial pressure (reaction order of 0.79) and a weaker dependence on CO 2 partial pressure (reaction order of 0.33) under equimolar flow of both reactants. X-ray powder diffraction patterns and XPS spectra reveal that the bulk structure of the post-reaction sample was mostly metallic Fe and Fe 3 C while the surface contained Fe 2+, Fe 3+, metallic Fe, and Fe 3 C. The activity test on pure Fe 3 C (iron carbide) suggests that Fe 3 C may not be the major active sites. Gas-switching experiments (CO 2 or H 2 ) indicated that a redox mechanism is the predominant reaction pathway, but the inverse kinetic isotope effect suggested a secondary pathway for CO formation, which is probably the so-called associative mechanism. Potential reaction mechanisms for this reaction were analyzed. [1] W. Wang, S. Wang, X. Ma, J. Gong, Recent advances in catalytic hydrogenation of carbon dioxide, Chem Soc Rev. 40 (2011) [2] J.A. Loiland, M.J. Wulfers, N.S. Marinkovic, R.F. Lobo, Fe/γ-Al 2 O 3 and Fe K/γ-Al 2 O 3 as reverse water-gas shift catalysts, Catal. Sci. Technol. 6 (2016) [3] D.H. Kim, S.W. Han, H.S. Yoon, Y.D. Kim, Reverse water gas shift reaction catalyzed by Fe nanoparticles with high catalytic activity and stability, J. Ind. Eng. Chem. 23 (2014) Page 21

23 CCST 2016 RESEARCH REVIEW Copper(I) Catalyzed Enantioselective Alkynylation of Oxocarbenium and Iminium Ions to set Diaryl Tetrasubstituted Stereocenters Srimoyee Dasgupta Advisor: Mary P. Watson The primary focus of our research group is to develop new synthetic methodologies that utilize the power of transition metal catalysis. Transition metal catalysis has transformed the field of synthetic organic chemistry by enabling new and highly efficient reactions with exceptional control over regio- and enantioselectivity. Most transition metal catalysis relies heavily on neutral electrophiles, but we envisioned that it could also be efficiently used with cationic electrophiles to solve significant, long-standing challenges in organic synthesis. In particular, few methods are available for enantioselective additions to cyclic ketoxocarbenium and ketiminium ions to form diaryl, tetrasubstituted stereocenters. Harnessing our success in developing a copper-catalyzed addition of terminal alkynes to oxocarbenium ions to deliver isochromans with tertiary stereocenters, 1 we have now developed a highly enantioselective, copper(i)/pybox-catalyzed addition of terminal alkynes to isochroman ketals to set diaryl-substituted quaternary stereocenters. 2 The success of this transformation relies on identification of a Cu/PyBox catalyst capable of distinguishing two aryl substituents on the forming stereocenter, which differ predominantly in their freedom of rotation and by their relationship to the oxygen substituents (alkyl vs lone pair). This highly challenging transformation enables the efficient conversion of readily available, racemic ketals to high-value, enantioenriched isochroman products, presumably via prochiral oxocarbenium ion intermediates. Reaction optimization, scope of both the ketal and alkyne, and elaboration of products will be presented. We were also able to use this potent copper(i)/pybox catalyst to develop an enantioselective, copper(i)-catalyzed alkynylation of ketiminium ion intermediates to deliver tetrahydroisoquinolines with tetrasubstituted α stereocenters in high yields and enantioselectivities. Select substrate scope and elaboration of products in this method will also be presented. We are currently investigating how the chiral copper/pybox catalyst imparts enantioselectivity in these reactions. Initial mechanistic experiments elucidating the structure of the active catalyst as a dicopper acetylide species and further reactions inspired by these methods will also be discussed. 1. (a) Maity, P.; Srinivas, H. D.; Watson, M. P. J. Am. Chem. Soc. 2011, 133, 17142; (b) Srinivas, H. D.; Maity, P.; Yap, G. P. A.; Watson, M. P. J. Org. Chem. 2015, 80, Dasgupta, S.; Rivas, T.; Watson, M. P. Angew. Chem. Int. Ed. 2015, 54, Page 22

24 CCST 2016 RESEARCH REVIEW Hydrodeoxygenation of Long-Carbon Trifurylmethane into Jet Fuels with Pd/C-Hf(OTf) 4 Dr. Saikat Dutta Advisor: Prof. Basudeb Saha, Prof. Dionisios G. Vlachos Beyond fossil-based hydrocarbons such as heavy oil, shale gas, and oil sands that protect global fossil fuel production, constituted development of renewable alternatives to petrochemicals production not only reduces dependence on finite crude oil but also take us one-step ahead for an energy secure future. 1 To overcome logistic problems of replacing fuel infrastructures that is already in place, accessing linear and branched alkanes for transportation fuel from biomass-derived molecules will be desired strategy. 2 Controlled removal of oxygen-containing functional groups from these biomass-derived molecules using common reagents and catalysts offer alkanes in good yields and high selectivity. 3 Catalytic defunctionalization of oxygen groups by reducing C-O bonds to C-H bonds known as hydrodeoxygenation (HDO) which increases energy density of the resulting molecule by reducing oxygen contents. Here, we describe the catalytic HDO of a long carbon trifurylmethane (C 15 ) derivative (1) using palladium on carbon (Pd/C) as catalyst in combination with hafnium triflate (Hf(OTf) 4 ) in cyclohexane which offers C15 and C14 alkanes as major products (Scheme 1). We reveal the roles of Pd nanoparticles on carbon support and Hf(OTf) 4 for the HDO of (1). Time profile of obtained products and intermediates and additional experimental results suggests the reaction progresses via rapid hydrogenation of (1) to a saturated furan derivative which then transformed to alkane products via ring-opening-oxygen removal event. Scheme 1. HDO of trifurylmethane (1) References: 1. Murray et al. Nature 2012, 481, King et al. ACS Catal. 2015, 5, Sutton et al. Nature Chem. 2013, 5, 428. Page 23

25 CCST 2016 RESEARCH REVIEW Heterogeneous Catalytic Route towards Succinic Acid from Biorenewable Tartaric Acid Jiayi Fu Advisor: Dionisios G. Vlachos Succinic acid (C4H6O4), a 4-C dicarboxylic acid, is recognized by DOE as one of the top value-added platform chemicals that can be derived from biomass. 1 It can replace malic acid and malic anhydride to produce valuable commodities chemicals, such as tetrahydrofuran, γ-butyrolactone and 1,4-butanediol.2 In industry, the production of succinic acid relies on fossil fuels, which brings negative impacts on environment and energy security. 3 Fermentation has been proposed as a renewable alternative with a better environmental footprint, yet the process is not economically completive due to the high purification cost. 2,4 Here, we propose a heterogeneous catalytic route to succinic acid using tartaric acid (C4H6O6) as the substrate. Tartaric acid occurs naturally in grapes and can be recovered from the waste of winery industry. 5 In this study, we show that in a mixture of hydrobromic acid and acetic acid partially reduced molybdenum oxide is an effective hydrodeoxygenation (HDO) catalyst that can selectively cleave the C-O bonds at C2 and C3 positions of tartaric acid. Currently, the best yield is 67% at 170 C under 40 bar of hydrogen. A time evolution study as well as controlled experiments using intermediate species and products as reactants provide insights into the reaction pathways and mechanism, which can guide in depth understanding and efficient process design. OH O HO + 2H OH 2 O OH Scheme 1. Production of succinic acid from the HDO of tartaric acid. O MoO x /Black Carbon HO + OH 2H 2 O 0.1 M HBr in Acetic Acid O Tartaric Acid Succinic Acid (1) Werpy, T. and Petersen, G. Top Value Added Chemicals from Biomass; (2) Carlson, A.; Coggio, B.; Lau, K.; Mercogliano, C.; Millis, J. 2016; pp (3) Gallezot, P. Chem. Soc. Rev. 2012, 41 (4), (4) Cheng, K. K.; Zhao, X. B.; Zeng, J.; Wu, R. C.; Xu, Y. Z.; Liu, D. H.; Zhang, J. A. Appl. Microbiol. Biotechnol. 2012, 95 (4), (5) Versari, A.; Castellari, M.; Spinabelli, U.; Galassi, S. J. Chem. Technol. Biotechnol. 2001, 76 (5), Page 24

26 CCST 2016 RESEARCH REVIEW Mechanistic Insights into the Ring Opening of Biomass-Derived Tetrahydrofuran-2,5-Dicarboxylic Acid to Adipic Acid Matthew J. Gilkey Advisors: Bingjun Xu and Dionisios G. Vlachos Adipic acid (AA) is an essential precursor in the polymer industry, primarily for its use in the synthesis of Nylon-66. However, AA s current production method, which relies on the selective oxidation of petroleum-derived cyclohexane, contains several drawbacks including the emission of N 2 O, a potent greenhouse gas. In effort to create a sustainable route to AA, significant research effort has been dedicated to develop pathways from biomass-derived platform chemicals through selective hydrodeoxygenation. Of particular interest is the hydrogenolytic ring opening of tetrahydrofuran-2,5-dicarboxylic acid (THFDCA) to AA. By reacting THFDCA in a mixture of hydriodic acid (HI) and molecular hydrogen in an organic acid solvent, an AA yield of up to 87% yield can be achieved in the absence of a metal catalyst. Through a combination of experimental and theoretical contributions, we reveal key mechanistic insights into the hydrogenolysis mechanism, noting that the nature of the solvent is critical in maintaining high ring opening activity. Due to the corrosive nature of HI and organic acids, however, the development of active, heterogeneous catalysts is desired to take the place of HI. Here, I will present our mechanistic understanding of HI-mediated ring opening and our ongoing work in designing solid materials for effective AA production. Page 25

27 CCST 2016 RESEARCH REVIEW Solvent Effects on Zeolites: Liquid Phase FTIR Extinction Coefficient Determination Nicholas Gould Advisor: Bingjun Xu Fundamental understanding of solvent effects, including how solvent choice affects catalyst structure, catalyst acidity, and product distributions is still lacking. To provide insight, attenuated total reflection (ATR) Fourier transform infrared spectroscopy (FTIR) was used to study the in-situ interactions between solvent, substrate, and catalyst. Specifically, pyridine was used as a probe molecule to characterize the relative ease of protonation in commonly used solvents. This has been used to understand how solvent choice affects substrate protonation and activity in Brønsted acid catalyzed reactions. However, the FTIR technique is limited by its inability to quantify adsorbed and bulk species. Quantitative FTIR requires integrated molar extinction coefficients (IMEC), or the amount of signal per mole of adsorbed or bulk species. A method has been established for vapor phase IMECs, 1 but liquid phase IMECs are still missing. A simple method is outlined for calculating extinction coefficients of pyridine adsorbed on zeolites in the liquid phase in an ATR cell. The same technique is also applicable to other substrates than pyridine. Liquid phase IMECs allow for future quantification of adsorbates in the liquid phase, improving the robustness of the ATR-FTIR technique, and opening the door to quantitative studies of how solvent choice affects substrate protonation by zeolites and other solid acids. The extinction coefficients for pyridine adsorbed on Brønsted and Lewis acid sites in water, ethanol, and acetonitrile were derived. The IMEC values are shown to be dependent on solvent choice, but independent of zeolite framework. These values will be used to quantify protonated pyridine in commonly used solvents. A Brønsted acid catalyzed dehydration reaction in these solvents will be used to correlate the protonation to activity. This The ATR-FTIR technique also showed the probe molecule, pyridine, getting protonated on sodium faujasite (NaY) in the presence of liquid water. 2 This is an example of how ATR-FTIR detected a solvent induced modification of catalyst surface structure. The NaY was shown to be crucial to the production of protonated species in water and to the accumulation of pyridinium in its pores. This is an occurrence usually only associated with proton form zeolites, such as HY. 1. Emeis, C. A. J. Catal. 141, Gould, N. S.; Xu, B. J. Catal. 342, Page 26